Departamento de Química, Universidad Politécnica de Valencia, C/Camino de Vera, s/n, 46022 Valencia, Spain.
ChemSusChem. 2011 May 23;4(5):650-7. doi: 10.1002/cssc.201000453. Epub 2011 Mar 23.
Gold nanoparticles supported on Fenton-treated diamond nanoparticles (Au/DNPs) have been reported as one of the most efficient solid catalysts effecting the Fenton reaction, achieving a turnover number (TON) as high as 321,000. However, at room temperature the main limitation for the catalytic activity of Au/DNPs is the pH of the solution, which should be less than 5. In this paper, we report that exposure of Au/DNPs to sunlight enhances the catalytic activity of Au/DNPs up to the point that it can promote the Fenton reaction at room temperature even at slightly basic pH values. Also, in addition to performing a deep Fenton treatment and considering that the excess of H(2)O(2) used in the process should be minimized, we have achieved in our study, using a mild Fenton reaction promoted by Au/DNPs under sunlight irradiation, an optimum in the biodegradability, a minimum in the ecotoxicity, and no toxicity for the Vibrio fischeri test. The results have shown that, by using an H(2)O(2) -to-phenol molar ratio of 5.5 or higher, it is possible to achieve a high biodegradability as well as a complete lack of ecotoxicity and of Vibrio fischeri toxicity. The stability of Au/DNPs was confirmed by analyzing the gold leached to the solution and by performing four consecutive reuses of the catalyst with initial pH values ranging from 4 to 8. It was observed that, after finishing the reaction and exhaustive washings with basic aqueous solutions, the initial reaction rate of the used catalyst is recovered to the value exhibited by the fresh solid. Overall, our study shows that the synergism between catalysis and photocatalysis can overcome the limitations found for dark catalytic reactions and that the reaction parameters can be optimized to effect mild Fenton reactions aimed at increasing biodegradability in biorecalcitrant waste waters.
负载在芬顿处理的金刚石纳米粒子(Au/DNPs)上的金纳米粒子已被报道为最有效的固体催化剂之一,可有效地实现芬顿反应,其转化数(TON)高达 321,000。然而,在室温下,Au/DNPs 催化活性的主要限制因素是溶液的 pH 值,其应小于 5。在本文中,我们报告 Au/DNPs 暴露于阳光下可增强 Au/DNPs 的催化活性,以至于即使在略微碱性的 pH 值下,也可以在室温下促进芬顿反应。此外,除了进行深度芬顿处理并考虑到应尽量减少过程中使用的过量 H2O2 之外,我们在研究中还通过在阳光下使用 Au/DNPs 促进温和的芬顿反应,实现了最佳的生物降解性、最小的生态毒性以及对发光菌测试的无毒性。结果表明,通过使用 H2O2 与苯酚的摩尔比为 5.5 或更高,可以实现高生物降解性以及完全没有生态毒性和发光菌毒性。通过分析浸出到溶液中的金以及在初始 pH 值范围为 4 至 8 的情况下连续重复使用催化剂四次,证实了 Au/DNPs 的稳定性。观察到,在完成反应并使用碱性水溶液进行彻底洗涤后,用过的催化剂的初始反应速率恢复到新鲜固体所表现出的速率。总体而言,我们的研究表明,催化和光催化之间的协同作用可以克服暗催化反应的局限性,并且可以优化反应参数以实现温和的芬顿反应,旨在增加生物难降解废水中的生物降解性。